US9683111B2 - Solution-processable tungsten oxide buffer layers and electronics comprising same - Google Patents
Solution-processable tungsten oxide buffer layers and electronics comprising same Download PDFInfo
- Publication number
- US9683111B2 US9683111B2 US14/378,631 US201314378631A US9683111B2 US 9683111 B2 US9683111 B2 US 9683111B2 US 201314378631 A US201314378631 A US 201314378631A US 9683111 B2 US9683111 B2 US 9683111B2
- Authority
- US
- United States
- Prior art keywords
- water
- composition
- nanoparticles
- solvent
- tungsten oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims description 55
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 135
- 239000000203 mixture Substances 0.000 claims description 129
- 239000002105 nanoparticle Substances 0.000 claims description 62
- 239000002904 solvent Substances 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 51
- 239000003960 organic solvent Substances 0.000 claims description 51
- 239000000725 suspension Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract description 7
- 238000013086 organic photovoltaic Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 53
- 239000010408 film Substances 0.000 description 43
- 239000000758 substrate Substances 0.000 description 29
- 229960004592 isopropanol Drugs 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- 239000010409 thin film Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000000137 annealing Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 7
- 239000011368 organic material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007764 slot die coating Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000007649 pad printing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- 102100023266 Dual specificity mitogen-activated protein kinase kinase 2 Human genes 0.000 description 1
- 101710146529 Dual specificity mitogen-activated protein kinase kinase 2 Proteins 0.000 description 1
- -1 ITO Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 0 [1*]O[2*]O Chemical compound [1*]O[2*]O 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001314 profilometry Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007560 sedimentation technique Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C09D7/001—
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- H01L51/00—
-
- H01L51/4213—
-
- H01L51/5088—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K99/00—Subject matter not provided for in other groups of this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/219—CrOx, MoOx, WOx
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02581—Transition metal or rare earth elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02601—Nanoparticles
-
- H01L2251/303—
-
- H01L2251/5369—
-
- H01L51/42—
-
- H01L51/5068—
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/30—Devices controlled by radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/157—Hole transporting layers between the light-emitting layer and the cathode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y02P70/521—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
Definitions
- the present invention relates to the field of organic electronics, such as OLEDs and OPVs. It particularly provides intermediates and materials suitable for manufacturing such organic electronics, to specific manufacturing methods and to specific uses.
- buffer layers in organic electronics, such as organic light emitting diodes (OLED) or organic photovoltaic cells (OPV), in order to increase device efficiency.
- OLED organic light emitting diodes
- OCV organic photovoltaic cells
- Such layers typically have a thickness below 100 nm to retain optical transparency and a low serial resistance.
- Such layers may comprise WO 3 and/or MoO 3 , which exhibit remarkably deep lying electronic states and are strongly n-doped by oxygen vacancies.
- Meyer et al. (Adv. Mater. 2008, 20, 3839-3843) disclose efficient hole-injection into organic materials with deep-lying HOMO levels from an ITO electrode covered with a MoO 3 or WO 3 hole injection layer (HIL) (also called hole transport layer (HTL)). Simplified device structures consisting only of one or two organic layers can therefore be realized.
- MoO 3 and WO 3 hole injection layers mentioned above are typically manufactured by thermal evaporation under high vacuum; which is disadvantageous in terms of low-cost, large
- This non-volatile organic material has a negative impact on the electronic properties of the HIL layer because all the inorganic HIL nanoparticles are covered with an electrically insulating organic shell. Therefore, an additional cleaning treatment by temperature annealing (>300° C.) or a plasma treatment (e.g. ozone plasma) is required which can damage organic functional layers and substrates.
- a plasma treatment e.g. ozone plasma
- Nakano et al. (US2011212832) describe water based WO 3 dispersions. Due to the fact that WO 3 exhibits an isoelectric point at about pH 1, the WO 3 particles are negatively charged at pH 7 in water resulting in electrostatic particle stabilization. However, such dispersions are of limited use, as they cannot be applied on hydrophobic substrates such as organic active layers, particularly due to the bad wettability of aqueous systems on such substrates. Further, Nakano et al. discuss addition of ethanol (up to 20 wt %) but find this embodiment disadvantageous due to aggregation and stability problems.
- Angiuli et al. (WO2007094019) describe colloidal solutions of tungsten oxide obtained by sol-gel methods and their application for the fabrication of thick WO 3 films used in thermochromic films. They achieve enhanced film formation on inorganic substrates by the use of an organic thickener (polyethylene glycol) and organic surfactants. Such WO 3 colloidal solutions are disadvantageous since the organic additives (thickener and surfactants) have a highly negative influence on the electronic properties of deposited WO 3 films.
- Tofonuko et al. (EP2360220) describe infrared blocking particle dispersions.
- the particles disclosed therein have a diameter in the range of 1-800 nm and are of tungsten oxide coated with tetrafunctional silanes, its hydrolysis product and/or organic metal compounds.
- the document is silent about the use in OPVs or OLEDs; it also does not disclose or discuss uncoated tungsten oxide (i.e. nanoparticles having a tungsten oxide surface).
- Harada et al. disclose organic electroluminescence elements and methods of manufacturing such elements. These elements comprise an HEL layer (4) or tungsten oxide. However, this layer is manufactured in a different process when compared to the present invention, at least because it does not disclose the suspensions of the present invention.
- composition as defined in claim 1 and a method of claim 7 .
- Further aspects of the invention are disclosed in the specification and independent claims, preferred embodiments are disclosed in the specification and the dependent claims.
- azeotrope is known in the field and describes mixtures of two or more liquids where the liquid phase and its vapor phase have the same ratio of constituents when boiling.
- the term includes both positive and negative azeotropes, binary and multiple azeotropes, as well as homogeneous and heterogeneous azeotropes.
- Positive/negative azeotropes Each azeotrope has a characteristic boiling point.
- the boiling point temperature of an azeotrope is either lower than the boiling point temperatures of any of its constituents (a positive azeotrope), or higher than the boiling point temperatures of any of its constituents (a negative azeotrope).
- a positive azeotrope boils at a lower temperature than any other ratio of its constituents.
- Positive azeotropes are also called minimum boiling mixtures or pressure maximum azeotropes.
- a well known example of a positive azeotrope is 95.6% ethanol and 4.4% water (by weight).
- ethanol boils at 78.4° C. water boils at 100° C., but the azeotrope boils at 78.2° C., which is lower than either of its constituents. Indeed 78.2° C. is the minimum temperature at which any ethanol/water solution can boil at atmospheric pressure. Preferred are positive azeotropes.
- Heterogeneous/homogeneous azeotropes If the constituents of a mixture are not completely miscible the azeotropic composition can be found inside the miscibility gap. This type of azeotrope is called heterogeneous azeotrope. If the azeotropic composition is outside the miscibility gap or the constituents of the mixture are completely miscible the type of azeotrope is called a homogeneous azeotrope.
- a heterogeneous azeotrope typically is indicated by three different azeotropic compositions including an average, an upper and a lower azeotropic composition.
- 1-butanol forms a heterogeneous azeotrope with water, having an average azeotropic composition of 44.5 wt % water, an upper azeotropic composition of 20.1 wt % water and a lower azeotropic composition of 92.3 wt % water.
- the average azeotropic composition of 44.5 wt % water is found in the miscibility gap of the 1-butanol/water system.
- the upper and lower azeotropic compositions are outside of the miscibility gap, forming homogeneous mixtures.
- azeotropic composition relates either to azeotropic compositions of homo-azeotropes (homogeneous azeotropes) or upper azeotropic compositions of hetero-azeotropes (heterogeneous azeotropes).
- aqueous azeotropes is known in the field and includes azeotropes where one component is water.
- azeotropic water content denotes the mass of water in a defined amount of a binary azeotropic composition (water content at the azeotropic point (a.p.)).
- azeotropic water content corresponding to 100 g of ethanol is 4.6 g because the azeotropic point is at 4.4 wt % water for the binary ethanol/water system.
- azeotropic water content is limited to one single organic solvent, regardless of the presence of another organic solvent. Two different organic solvents present in a homogeneous solvent composition therefore result in two different azeotropic watercontents (one for each solvent).
- total azeotropic water content denotes the sum of all azeotropic water contents in a solvent composition.
- the azeotropic water content total azeotropic water content.
- organic solvent is known in he field and particularly includes alcohols, nitriles, ketones, esters, ethers, aldehydes. Except for alcohols, the above derivatives are preferably non-substituted. Alcohols may be partly or fully substituted with halogen. Alcohols may be partly substituted with alkoxy. Alcohols may also contain multiple bonds.
- the above derivatives include linear, branched and cyclic derivatives. The above derivatives typically have 1-12 carbon atoms, preferably 1-5 carbon atoms.
- amount of organic solvent denotes the mass of a specific organic solvent present in a solvent composition (i.e. 10 g (ethanol)).
- total amount of organic solvent denotes the weight-based sum of all portions of organic solvents in a given amount of a final composition (i.e. 50 g (i.e. 10 g ethanol+40 g 1-propanol)).
- amount of water denotes the weight-based total portion of water in a given amount of a final composition (i.e. 50 g (water)).
- surfactant refers to an organic substance, other than a solvent, which is used in suspensions or colloids to improve the separation of particles and to prevent agglomeration or settling.
- Surfactants, dispersants and dispersing agents can be polymers or small molecules and typically contain functional groups. Surfactants, dispersants and dispersing agents are physically or chemically attached on the particle surface either before or after adding the particles to the external phase.
- water and organic solvent molecules e.g. ethanol, methanol or isopropanol are not considered surfactants, dispersants or dispersing agents.
- FIG. 1 shows a schematic set-up of the invention.
- the invention describes specific compositions containing tungsten oxide (COMP, 1 st aspect of the invention, denoted (I)) which enable the solution deposition of tungsten oxide nanoparticle layers on substrates (INT, 2 nd aspect of the invention; (II)).
- the obtained thin films show a low residual organic content after drying under moderate conditions (3 rd aspect). These layers are useful in the manufacturing of organic electronics (DEV).
- the above compositions are obtainable as described in the 4 th aspect of the invention (IV) by the use of known starting materials (S.M.)
- FIG. 2 shows the essential layers of an intermediate product (INT), useful for the manufacturing of organic electronics, wherein (1) is the tungsten oxide hole transport layer, (2) is an organic active layer (e.g. a polymeric active layer or a small-molecule active layer) and (3) is an electrode or a second organic active layer.
- the electrode can be transparent or non-transparent.
- the three depicted layers are only part of a more complex layer architecture forming an intermediate product; underneath or on top of the depicted layers can be different layers, such as a supporting substrate, and/or an electron transport layer and/or a second electrode.
- FIG. 3 shows a schematic illustration for an inventive suspension composition comprising tungsten oxide, organic solvent and water.
- the x-axis denotes the amount of water (wt-%), the azeotropic point (a.p.) is noted.
- the y-axis denotes the amount of nanoparticles (wt-%), preferred upper and lower limits are indicated.
- the amount of water is below the azeotropic water/organic solvent composition and the ratio of nanoparticles/water is within the indicated range.
- the grey area indicates inventive compositions; Such compositions show improved stability, wettability and film formation.
- FIG. 4 shows a schematic illustration for an alternative inventive suspension composition comprising tungsten oxide, organic solvent and water.
- the x-axis denotes the amount of water (wt-%), which may be up to 10% above the azeotropic point, the azeotropic point (a.p.) is noted.
- the y-axis denotes the amount of nanoparticles (wt-%), preferred upper and lower limits are indicated.
- the amount of water is up to 10 wt % above the azeotropic water/organic solvent composition and the ratio of nanoparticles/water is within the indicated range.
- the grey area indicates inventive compositions.
- Such compositions also show improved stability, wettability and film formation.
- the invention in more general terms, in a first aspect, relates to a composition in the form of a suspension, said composition containing (a) tungsten oxide nanoparticles as described below, and (b) a homogeneous solvent composition as described below as type (A), (B) and (C).
- the homogeneous solvent composition contains water. Without being bound to theory, it is believed water stabilizes the nanoparticles (a) and thus facilitates the further processing.
- compositions described herein as type (A), (B) and (C) and (D) have beneficial properties and have advantageous uses as outlined below. It was found that the inventive compositions (i) show good wettability on both hydrophobic substrates (such as organic functional layers) and hydrophilic substrates (such as ITO, glass); and/or (ii) are compatible with organic materials, particularly no swelling or dissolution of organic materials is observed; and/or (iii) show a high shelf-life (superior suspension stability); and/or (iv) show homogeneous film formation on hydrophobic and hydrophilic substrates.
- hydrophobic substrates such as organic functional layers
- hydrophilic substrates such as ITO, glass
- suspension is known and relates to a heterogeneous fluid of an internal phase (i.p.) that is a solid and an external phase (e.p.) that is a liquid.
- a suspension typically has a kinetic stability of at least 1 day (measured according to complete particle sedimentation).
- the invention provides for a composition with (hydrodynamic size D 90 of less than 100 nm) a shelf-life of more than 7 days, particularly more than 2 months.
- Tungsten oxide nanoparticles include (i) nanoparticles of pure tungsten oxide, (ii) nanoparticles of doped tungsten oxide and (iii) core shell nanoparticles, whereby the shell is composed of tungsten oxide or doped tungsten oxide and whereby the core is composed of a different inorganic material.
- nanoparticle is known and particularly relates to solid amorphous or crystalline particles having at least one dimension in the size range of 1-100 nm.
- nanoparticles are approximately isometric (such as spherical or cubic nanoparticles). Particles are considered approximately isometric, in case the aspect ratio (longest: shortest direction) of all 3 orthogonal dimensions is 1-2.
- the nanoparticles have a mean primary particle size of 2-60 nm, preferably 5-30 nm (measured by transmission electron microscopy).
- the nanoparticles in suspension have a hydrodynamic size D 90 of less than 100 nm (measured by dynamic light scattering or centrifugal sedimentation techniques).
- the nanoparticles are synthesized by a gas phase process, preferably flame spray synthesis.
- a gas phase process preferably flame spray synthesis.
- the microstructure of such nanoparticles differs from the microstructure of particles synthesized e.g. by precipitation processes or by sublimation processes.
- Compositions as described herein and comprising particles made by gas phase processes are particularly stable and suitable in the applications described below.
- the amount of nanoparticles in the inventive composition may—depending on the intended use—vary over a broad range, but typically is in the range of 0.1-20 wt % (preferably 0.1-10 wt %, particularly preferably 1-5 wt %) of the composition.
- the nanoparticle solid content of the corresponding composition should be comparatively low.
- the final nanoparticulate film thickness can be reduced to small values well below 100 nm.
- water is known and particularly relates to purified water, such as de-ionized or distilled water.
- the amount of water in the inventive composition may—depending on the intended use—vary over a broad range, but typically is in the range of 0.1-20 wt %, especially 0.5-10 wt % of the composition. It was surprisingly found that this low amount of water is sufficient for stabilizing the nanoparticles.
- the suspension stability is very high if all the water present in a formulation forms an azeotropic interaction with a solvent.
- the suspension stability is high if the amount of water is below the azeotropic composition for a water/solvent system.
- the amount of water should be below 4.4 wt % (azeotropic point of water in ethanol) with respect to ethanol (see FIG. 3 ).
- the suspension stability is high if the amount of water exceeds the azeotropic composition for a water/solvent system up to 10% wt-%.
- said homogeneous solvent composition contains, preferably consists of, (i) water; (ii) a first organic solvent forming a binary azeotrope with water;
- the homogeneous solvent composition (b) is chosen to contain water in such an amount that after azeotropic evaporation of the water, organic solvent remains.
- the amount of water in said solvent composition (b) is lower than the total amount of organic solvent.
- the composition in the “upper region”. Further, by this embodiment, the surface tension shows beneficial properties.
- said first solvent is selected from the group consisting of alcohols, and nitriles.
- said first solvent has a formula (I) R—OH (I) where R represents a linear or branched, non-substituted alkyl chain having 2-5 carbon atoms, preferably 2-4 carbon atoms, most preferably 2-3 carbon atoms.
- said first solvent is selected from the group consisting of Ethanol, 1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, iso-Butanol, tert-Butanol, acetonitrile, propionitrile.
- said homogeneous solvent composition of type (A) consists of water and a first organic solvent forming a positive azeotrope with water.
- said homogeneous solvent composition contains, preferably consists of, (i) water; (ii) a first organic solvent forming a binary azeotrope with water; (iii) additionally a second organic solvent forming a binary azeotrope with water,
- the homogeneous solvent composition (b) is chosen to contain water in such an amount that after azeotropic evaporation of the water, organic solvent remains.
- the amount of water in said solvent composition (b) is lower than the total amount of organic solvent.
- the composition in the “upper region”. Further, by this embodiment, the surface tension shows beneficial properties.
- said second solvent is selected from the group consisting of alcohols, nitriles, ketones, esters, ethers, aldehydes and alkoxy-alcohols.
- alkoxy-alcohols have a formula (II)
- R1 and R2 represent a linear or branched alkyl chain having 1 to 6 carbon atoms each and where the total number of carbon atoms is between 3 and 7.
- said homogeneous solvent composition contains, preferably consists of, (i) water; (ii) the first and optionally the second organic solvent (both as defined herein); and (iii) a third organic solvent not forming a binary azeotrope with water,
- the homogeneous solvent composition (b) is chosen to contain water in such an amount that after azeotropic evaporation of the water, organic solvent remains.
- the amount of water in said solvent composition (b) is lower than the total amount of organic solvent.
- the composition in the “upper region”. Further, by this embodiment, the surface tension shows beneficial properties.
- said third solvent is selected from the group consisting of alcohols, nitriles, ketones, esters, ethers, aldehydes and alkoxy-alcohols.
- alkoxy-alcohols have a formula (II) as defined above.
- said homogeneous solvent composition contains, preferably consists of, a composition as described in (A), (B), or (C) whereby the amount of water in said solvent composition (b) is up to 10% above the total azeotropic water content with respect to said first organic solvent.
- homogeneous solvent composition of type (A), (B), (C) or D may additionally contain one or more further organic solvents
- the homogeneous solvent compositions either consist of the components as described above or comprise these components and, for example, one further organic solvent.
- the invention provides a composition in the form of a suspension as defined herein, wherein the amount of water ⁇ total azeotropic water content; and the ratio of amount of nanoparticles:amount of water ⁇ 9:1; and the amount of nanoparticles in the total composition is in the range of 0.1-20 wt %.
- Suitable examples for inventive compositions are outlined in the table below:
- the suspension of the present invention (i.e. for types (A) to (D)) is free of, or essentially free of, surfactants and dispersing agents.
- the invention provides a composition as described herein (i.e. for types (A) to (D)) resulting in a residual organic carbon content of less than 2.5 wt %, particularly less than 1 wt %, this value being obtained after drying for 1 h at 150° C. after application by solution processing (e.g. roll-to-roll-coating or slot-die coating).
- the invention provides a composition as described herein (i.e. for types (A) to (D)) wherein the amount of homogeneous solvent composition is in the range of 80-99.9 wt %, preferably 90-99.9 wt %.
- the invention provides a composition as described herein (i.e. for types (A) to (D)) wherein said first solvent and/or said second solvent has a boiling point below 150° C.
- the invention provides a composition as described herein (i.e. for types (A) to (D)) wherein said first solvent and/or said second solvent has a surface tension below 30 mN/m.
- the invention provides a composition as described herein (i.e. for types (A) to (D)) wherein said nanoparticles consist of tungsten oxide having the chemical composition WO x (“pure tungsten oxide”).
- tungsten oxide having the chemical composition WO x (“pure tungsten oxide”).
- pure tungsten oxide” relates to compositions with the formula WO x , whereby x typically is 2-3.
- the invention provides a composition as described herein (i.e. for types (A) to (D)) wherein said WO x nanoparticles are doped with 0.001-30 wt %, preferably 0.01-10 wt %, most preferably 0.01-5 wt % (with respect to W), by one or more metals (“doped tungsten oxide”).
- the dopant atoms are incorporated into the WO x crystal lattice either substitutionally or interstitially forming a homogeneous single-phase (a “solid solution”).
- separated multiphase systems e.g. WO x +Fe 2 O 3
- doped tungsten oxide e.g. tungsten oxide
- said dopant atoms are selected from the group consisting of transition metals or alkaline or earth-alkaline metals.
- Doping of tungsten oxide can enable the fine tuning of the properties of the inventive thin films, such as electrical conductivity and/or optical absorbance.
- the invention provides a composition as described herein (i.e. for types (A), (B) and (C) and (D)) wherein said tungsten oxide nanoparticles are core-shell nanoparticles having a core-shell architecture.
- the shell is composed of tungsten oxide or doped tungsten oxide.
- the thickness of the shell typically is between a monolayer and 20 nm of tungsten oxide, preferably between 1 nm and 10 nm tungsten oxide.
- Deposition of tungsten oxide shells includes techniques such as atomic layer deposition or sol-gel methods.
- the core is composed of an inorganic material different from the shell. Suitable core materials are metal-oxides.
- the invention further provides for various uses of the inventive compositions. These include: (a) the use of tungsten oxide nanoparticle films as a hole transport layer in organic solar cells or in organic light emitting diodes or in organic photo detectors; (b) the use of tungsten oxide nanoparticle films in photochromic applications; (c) the use of tungsten oxide nanoparticle films as a catalytic active material (“a catalyst”). Further uses include the use in electrochromic applications; and/or thermochromic applications; and/or in sensor applications; and/or in a transistor; and/or in a varistor; and/or in a capacitor; and/or in thermoelectric applications.
- the invention in a second aspect, relates to a process for manufacturing thin films of nanoparticles.
- These films have beneficial properties and have advantageous uses as outlined below. It was found that the inventive films (i) are obtainable by a solution process; (ii) are essentially free of (or free of) residual organic materials after drying at a temperature below 150° C.; (iii) are thin (below 200 nm) (iv) have a low final surface roughness (below 100 nm). This aspect of the invention shall be explained in further detail below.
- the invention provides a method for manufacturing a thin film, comprising the steps of (a) applying a composition as described herein (i.e. type (A), (B) and (C) and (D)) on a substrate or coated substrate and (b) removing the solvent from said composition and optionally (c) treating the dried films at elevated temperature.
- a composition as described herein i.e. type (A), (B) and (C) and (D)
- Step (a) Application of a suspension: Many processes are known to apply a liquid composition to a substrate to result in a wet thin film; a person skilled in the art is in a position to appropriately select. Suitable are, for example roll-to-roll coating, slot-die coating, spray coating, dip coating, ink-jet printing, reel-to-reel coating, pad printing, offset printing, screen printing, sheet-to-sheet printing or blade coating. Such processes are generally considered advantageous for large scale production, when compared to vacuum-based processes. Depending on the composition used in step (a), this step may be repeated (i.e. may be performed multiple times). This embodiment is considered advantageous in order to fine tune the final film thickness.
- Step (b) Drying and film formation Many processes are known to remove a liquid from a wet thin film of a coated substrate; a person skilled in the art is in a position to appropriately select. Suitable are, for example drying at room temperature or elevated temperature. Drying may take place in air, in a protecting gas, such as nitrogen or argon. Especially suited are gases with low humidity content (e.g. N2, dry air, Ar).
- a protecting gas such as nitrogen or argon.
- gases with low humidity content e.g. N2, dry air, Ar.
- the annealing step is preferably conducted at a temperature above the highest boiling point with respect to all organic solvents in a suspension composition. In order to minimize the water content, an annealing step above 100° C. is preferred. The maximum annealing temperature is typically below 150° C. and is only limited by the temperature sensitivity of the substrate.
- the annealing step can be conducted in oxygen, air or in an oxygen-free atmosphere (“protecting gas”, e.g. N2 or Ar).
- the invention relates to a method as described herein, wherein said film has a thickness between 5-200 nm, preferably 10-150 nm (determined by electron microscopy).
- the invention relates to a method as described herein, wherein said film has a mean surface roughness below 100 nm, especially below 50 nm (determined by electron microscopy, atomic force microscopy or profilometry).
- the invention relates to a method as described herein, wherein said film has an electrical conductivity of 10 ⁇ ( ⁇ 6) ⁇ 10 ⁇ (4) S/cm, preferably 10 ⁇ ( ⁇ 4) ⁇ 10 ⁇ (2) S/cm (determined by 4-point conductivity measurement).
- the substrate referred to above is a hydro-phobic organic substrate, preferably a substrate with a surface free energy below 40 mJ/m 2 , particularly preferably below 30 mJ/m 2 .
- Such substrates may be uncoated or coated and include organic active layers ((2) in FIG. 2 ) as defined above.
- these thin films are either known or novel.
- the invention provides for an alternative manufacturing method of thin films, this method being advantageous over the known methods. For example, there is no need for a plasma-cleaning step of the as-deposited films (e.g. by ozone). Further, the thin film produced according to this embodiment, allows a defect-free production, particularly when deposited on hydrophobic substrates. Further, the thin film produced according to this embodiment, shows ⁇ 2.5 wt %, particularly ⁇ 1 wt %, residual organic carbon content when dried at temperatures below 150° C.
- the invention also provides for new films, being subject of the present invention.
- Such new thin films are characterized by one or more of the following parameters (i) being essentially free of (or free of) residual organic materials after drying at a temperature below 150° C.; (ii) having a thickness below 200 nm (iv) having a final surface roughness below 100 nm; and/or (iv) consist of nanoparticles obtained by a gas phase process.
- the invention further provides for a process of manufacturing organic electronics and electrical intermediates (both as defined herein), said process comprising the steps of providing a substrate; performing steps (a) and (b) and optionally (c) (as defined above); and optionally performing further coating steps. Due to the beneficial properties of the thin film (as defined herein), there is no need of performing plasma-cleaning (e.g. ozone plasma) after step (b) or (c) respectively.
- the invention also provides for a process of manufacturing organic electronics and electrical intermediates, said process comprising the steps of providing a substrate; performing steps (a),(b) and/or (c); and optionally performing further coating steps, wherein no plasma-cleaning takes place after step (b) or (c) respectively.
- the invention further provides for a process of manufacturing organic electronics and electrical intermediates (both as defined herein), by solution processing.
- solution processing relates to the fabrication of organic electronics and electrical intermediates comprising thin nanoparticle films by the use of one or more liquid suspensions, characterized in that the application of the suspension(s) is/are conducted preferably at ambient pressure.
- the invention relates to an electrical element (intermediate, INT), comprising one or more, preferably one, thin film as described herein or obtained by a method as described herein. Further, the invention relates to a device comprising one or more of such elements. This aspect of the invention shall be explained in further detail below.
- organic electronics are known in the field and relate to electronic devices comprising a substrate and a multitude of layers, wherein at least one layer is a buffer layer, particularly a hole transport layer (HTL). Depending on the remaining layers, its structure and connection, these devices serve a multitude of purposes, such as an OLED, an OPV, an organic photo detector or a tandem solar cell.
- OLED organic light emitting diode
- OLED organic photo detector
- buffer layer is known in the field and denotes an interface layer in electronic devices, typically in OPV or OLED devices.
- the term buffer layer includes both, electron selective buffer layers and hole selective buffer layers.
- Buffer layer also denoted ‘charge selective layer’ or ‘charge transport layer’, is the general term for layers with different electronic functions and particularly includes hole transport layers (HTL), hole injection layers (HIL), hole extraction layers (HEL), electron transport layers (ETL), electron injection layers (EIL) or electron extraction layers (EEL).
- the invention relates to a device comprising one or more electrical elements as described herein, preferably selected from the group of organic electronics, particularly an organic solar cell (OPV), an organic light emitting diode (OLED), an organic photo detector or a tandem solar cell.
- OLED organic solar cell
- OLED organic light emitting diode
- the invention relates to an OLED wherein the HTL (i) is obtained by a method as described herein or (ii) consists of a thin layer as described herein.
- the OLED preferably comprises a substrate selected from the group of organic polymers.
- the invention relates to an organic solar cell (OPV) wherein the HTL (i) is obtained by a method as described herein or (ii) consists of a thin layer as described herein.
- the OPV preferably comprises a substrate selected from the group of organic polymers, metals or oxides.
- the invention relates to an OPV or OLED device where the hole transport layer is applied between the anode and the organic active layer (inverted architecture).
- the invention relates to an OPV or OLED device where the hole transport layer is applied between the cathode and the organic layer.
- the invention relates to an OPV device with tandem architecture.
- the invention relates to a method for manufacturing a composition as described herein. This aspect shall be explained in further detail below.
- the invention relates to a method for manufacturing a composition as described herein (c.f. FIG. 1 ), comprising the steps of (a) providing a homogeneous solvent composition (S.M.), (b) providing nanoparticles (S.M), (c) combining said nanoparticles with said homogeneous solvent composition to obtain a suspension (COMP.).
- Tungsten oxide nanoparticles with a nominal composition of WO 3 were synthesized by flame spray synthesis.
- 42 g of sodium metatungstate (Fluka) was dissolved in 750 g distilled water and 75 g acetic acid. After adding 225 g aniline the solution was manually shaken for 3 min and washed three times with water in order to remove sodium and acetic acid. The obtained solution was diluted with THF 1:2 by weight.
- the precursor then was fed (5 ml min ⁇ 1 , HNP Mikrosysteme, micro annular gear pump mzr-2900) to a spray nozzle, dispersed by oxygen (7 l min ⁇ 1 , PanGas tech.) and ignited by a premixed methane-oxygen flame (CH 4 :1.2 l min ⁇ 1 , O 2 :2.2 l min ⁇ 1 ).
- the off-gas was filtered through a glass fiber filter (Schleicher & Schuell) by a vacuum pump (Busch, Seco SV1040CV) at about 20 m 3 h ⁇ 1 .
- the obtained tungsten oxide nanopowder was collected from the glass fiber filter.
- tungsten oxide nanopowder For the preparation of the tungsten oxide suspension 2 wt % of tungsten oxide nanopowder (as described above) was dispersed by ball-milling for 60 min in a mixture of 2 wt % distilled water and 96 wt % dry ethanol. The finally prepared suspension is transparent and stable for more than 3 months. After 3 months, the hydrodynamic particle size (D 99 ) was determined as 37 nm (measured by a centrifugal particle sizer (Lumisizer)).
- Tungsten oxide nanoparticle films were spin-coated on HDPE and PVC foils under nitrogen resulting in homogeneous and defect-free tungsten oxide films.
- the thickness of the deposited tungsten oxide films was determined as ⁇ 50 nm by scanning electron microscopy (SEM). The surface roughness was estimated to be in the range of 5-10 nm (SEM). Annealing of the obtained films for 30 min at 130° C. in air resulted in a residual organic carbon content (microanalysis) of 0.5 wt %.
- a stabilized tungsten oxide suspension was obtained by dispersing 2 wt % of tungsten oxide (as described above) in a mixture of 95 wt % dry isopropanol and 3 wt % of distilled water without further addition of an organic surfactant or dispersing agent. After 3 months, the hydrodynamic particle size (D 99 ) was determined as 32 nm (measured by a centrifugal particle sizer (Lumisizer)).
- the coated material After suspension application the coated material is dried under nitrogen at room temperature and ambient pressure. During drying, an azeotropic water/isopropanol mixture (12.1 wt % water, 87.9 wt % isopropanol) evaporates first, leaving back isopropanol and tungsten oxide. (isopropanol prevents de-wetting of the still wet film composed of isopropanol and tungsten oxide.)
- isopropanol evaporates prior leaving a dry film of tungsten oxide, tungsten oxide and water-free isopropanol is not a stable suspension system, but the film drying at this stage is almost complete and tungsten oxide has no time to form loose agglomerates. As a result, a defect-free thin film with a thickness below 200 nm and a surface roughness below 100 nm is obtained, essentially free of residual organic materials.
- suspension stability is measured at ambient conditions, whereby the suspension stability is denoted “ ⁇ ” if more than 10% of tungsten oxide is sedimented between 0 and 1 day, “ ⁇ ” if more than 10% is sedimented between 1 day and 1 week, “+” if more than 10% is sedimented between 1 week and 2 months, “++” if less than 10% is sedimented after 2 months
- the films obtained according to experiments 4,5,9-11,14 16-18,25,27,28 are obtained by doctor-blading the corresponding suspensions in nitrogen on HDPE and PVC substrates. Drying of the wet was conducted for 5 min under nitrogen at room temperature and ambient pressure.
- the thus obtained films have a thickness of 50-100 nm, are defect free and exhibit a surface roughness below 50 nm (all as determined by electron microscopy).
- the thus obtained films have a residual organic carbon content of less than 1 wt % within the film.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- General Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Geochemistry & Mineralogy (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Photovoltaic Devices (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12001157.2 | 2012-02-22 | ||
EP12001157.2A EP2631008A1 (en) | 2012-02-22 | 2012-02-22 | Solution-processable tungsten oxide buffer layers and electronics comprising same |
EP12001157 | 2012-02-22 | ||
PCT/CH2013/000032 WO2013123605A1 (en) | 2012-02-22 | 2013-02-15 | Solution-processable tungsten oxide buffer layers and electronics comprising same |
Publications (2)
Publication Number | Publication Date |
---|---|
US20150064446A1 US20150064446A1 (en) | 2015-03-05 |
US9683111B2 true US9683111B2 (en) | 2017-06-20 |
Family
ID=47749587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/378,631 Active 2033-11-28 US9683111B2 (en) | 2012-02-22 | 2013-02-15 | Solution-processable tungsten oxide buffer layers and electronics comprising same |
Country Status (6)
Country | Link |
---|---|
US (1) | US9683111B2 (ko) |
EP (2) | EP2631008A1 (ko) |
JP (1) | JP6204378B2 (ko) |
KR (1) | KR102017092B1 (ko) |
CN (1) | CN104245124B (ko) |
WO (1) | WO2013123605A1 (ko) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014103290A (ja) * | 2012-11-21 | 2014-06-05 | Konica Minolta Inc | 有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス素子の製造方法及び金属酸化物粒子含有組成物 |
FR3013719B1 (fr) * | 2013-11-26 | 2018-01-12 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Encre pour former des couches p dans des dispositifs electroniques organiques |
KR102074599B1 (ko) * | 2015-07-31 | 2020-02-06 | 아반타마 아게 | 발광성 결정 및 그의 제조 |
WO2019030269A1 (en) | 2017-08-09 | 2019-02-14 | Basf Se | COMPOSITIONS COMPRISING DISPERSED NANOPARTICLES OF ELECTROCHROMIC OXIDE |
CN108003664B (zh) * | 2017-12-04 | 2020-09-11 | 瑞彩科技股份有限公司 | 一种吸收红外的光热效应珠光颜料及其制备方法 |
JP7379306B2 (ja) * | 2020-09-28 | 2023-11-14 | 東芝マテリアル株式会社 | エレクトロクロミック素子 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5165992A (en) * | 1991-07-02 | 1992-11-24 | Hoya Corporation | Hard coating film and optical elements having such coating film |
US5366545A (en) * | 1992-07-07 | 1994-11-22 | Hoya Corporation | Coating compositions |
US5472797A (en) * | 1992-07-07 | 1995-12-05 | Hoya Corporation | Optical elements having cured coating film |
US6010778A (en) * | 1992-06-04 | 2000-01-04 | Nikon Corporation | Coating composition utilizing modified sol having tin oxide-tungsten oxide complex colloid particles and lens coated therewith |
JP2003334430A (ja) | 2002-05-17 | 2003-11-25 | Asahi Kasei Corp | 抽出方法 |
WO2007094019A1 (en) | 2006-02-17 | 2007-08-23 | Nm Tech Ltd. Nanomaterials And Microdevices Technology | A method for preparing nanocrystalline transparent films of tungsten oxide |
US20070290604A1 (en) | 2006-06-16 | 2007-12-20 | Matsushita Electric Industrial Co., Ltd. | Organic electroluminescent device and method of producing the same |
JP2009277601A (ja) | 2008-05-16 | 2009-11-26 | Dainippon Printing Co Ltd | 有機エレクトロルミネッセンス素子用基板および有機エレクトロルミネッセンス素子ならびにそれらの製造方法 |
US7708974B2 (en) * | 2002-12-10 | 2010-05-04 | Ppg Industries Ohio, Inc. | Tungsten comprising nanomaterials and related nanotechnology |
EP2360220A1 (en) | 2008-11-13 | 2011-08-24 | Sumitomo Metal Mining Co., Ltd. | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
US20110212832A1 (en) | 2008-03-04 | 2011-09-01 | Kabushiki Kaisha Toshiba | Aqueous dispersion liquid and coating material, film, and product using the same |
US20110317239A1 (en) | 2009-05-20 | 2011-12-29 | Katsuhiro Mori | Coating composition and optical article |
WO2012017502A1 (ja) | 2010-08-06 | 2012-02-09 | パナソニック株式会社 | 有機el素子およびその製造方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007094019A (ja) * | 2005-09-29 | 2007-04-12 | Kinki Sharyo Co Ltd | 広告吊り具 |
JP2008041894A (ja) * | 2006-08-04 | 2008-02-21 | Matsushita Electric Ind Co Ltd | 有機エレクトロルミネッセント素子およびその製造方法 |
EP2048116A1 (en) * | 2007-10-09 | 2009-04-15 | ChemIP B.V. | Dispersion of nanoparticles in organic solvents |
EP2781562B1 (en) * | 2013-03-20 | 2016-01-20 | Agfa-Gevaert | A method to prepare a metallic nanoparticle dispersion |
-
2012
- 2012-02-22 EP EP12001157.2A patent/EP2631008A1/en not_active Withdrawn
-
2013
- 2013-02-15 KR KR1020147025115A patent/KR102017092B1/ko active IP Right Grant
- 2013-02-15 WO PCT/CH2013/000032 patent/WO2013123605A1/en active Application Filing
- 2013-02-15 JP JP2014557955A patent/JP6204378B2/ja active Active
- 2013-02-15 US US14/378,631 patent/US9683111B2/en active Active
- 2013-02-15 EP EP13705901.0A patent/EP2817091B1/en active Active
- 2013-02-15 CN CN201380010676.2A patent/CN104245124B/zh active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5165992A (en) * | 1991-07-02 | 1992-11-24 | Hoya Corporation | Hard coating film and optical elements having such coating film |
US6010778A (en) * | 1992-06-04 | 2000-01-04 | Nikon Corporation | Coating composition utilizing modified sol having tin oxide-tungsten oxide complex colloid particles and lens coated therewith |
US5366545A (en) * | 1992-07-07 | 1994-11-22 | Hoya Corporation | Coating compositions |
US5472797A (en) * | 1992-07-07 | 1995-12-05 | Hoya Corporation | Optical elements having cured coating film |
JP2003334430A (ja) | 2002-05-17 | 2003-11-25 | Asahi Kasei Corp | 抽出方法 |
US7708974B2 (en) * | 2002-12-10 | 2010-05-04 | Ppg Industries Ohio, Inc. | Tungsten comprising nanomaterials and related nanotechnology |
WO2007094019A1 (en) | 2006-02-17 | 2007-08-23 | Nm Tech Ltd. Nanomaterials And Microdevices Technology | A method for preparing nanocrystalline transparent films of tungsten oxide |
US20070290604A1 (en) | 2006-06-16 | 2007-12-20 | Matsushita Electric Industrial Co., Ltd. | Organic electroluminescent device and method of producing the same |
US20110212832A1 (en) | 2008-03-04 | 2011-09-01 | Kabushiki Kaisha Toshiba | Aqueous dispersion liquid and coating material, film, and product using the same |
JP2009277601A (ja) | 2008-05-16 | 2009-11-26 | Dainippon Printing Co Ltd | 有機エレクトロルミネッセンス素子用基板および有機エレクトロルミネッセンス素子ならびにそれらの製造方法 |
EP2360220A1 (en) | 2008-11-13 | 2011-08-24 | Sumitomo Metal Mining Co., Ltd. | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
US20110317239A1 (en) | 2009-05-20 | 2011-12-29 | Katsuhiro Mori | Coating composition and optical article |
WO2012017502A1 (ja) | 2010-08-06 | 2012-02-09 | パナソニック株式会社 | 有機el素子およびその製造方法 |
US20130126848A1 (en) | 2010-08-06 | 2013-05-23 | Panasonic Corporation | Organic electroluminescence element and method of manufacturing thereof |
Non-Patent Citations (5)
Title |
---|
English translation of the details an Office Action in corresponding Japanese Application No. 2014-0557955 dated Dec. 2016. |
International Search Report for corresponding International Application No. PCT/CH2013/000032 mailed Apr. 29, 2013. |
Meyer et al., "MoO3 Films Spin-Coated from a Nanoparticle Suspension for Efficient Hole-Injection in Organic Electronics", Advanced Materials, vol. 23, 2011, pp. 70-73. |
Meyer et al., "Transparent Inverted Organic Light-Emitting Diodes with a Tungsten Oxide Buffer Layer", Advanced Materials, vol. 20, 2008, pp. 3839-3843. |
Stubhan et al., "High shunt resistance in polymer solar cells comprising a MoO3 hole extraction layer processed from nanoparticle suspension", Applied Physics Letters, vol. 98, 2011, pp. 253308-1 to 253308-3. |
Also Published As
Publication number | Publication date |
---|---|
US20150064446A1 (en) | 2015-03-05 |
KR20140125842A (ko) | 2014-10-29 |
CN104245124A (zh) | 2014-12-24 |
KR102017092B1 (ko) | 2019-09-02 |
EP2817091A1 (en) | 2014-12-31 |
WO2013123605A1 (en) | 2013-08-29 |
JP2015517198A (ja) | 2015-06-18 |
JP6204378B2 (ja) | 2017-09-27 |
EP2817091B1 (en) | 2016-11-30 |
CN104245124B (zh) | 2017-08-29 |
EP2631008A1 (en) | 2013-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9683111B2 (en) | Solution-processable tungsten oxide buffer layers and electronics comprising same | |
US10003037B2 (en) | Optoelectronic devices comprising solution-processable metal oxide buffer layers | |
Cheng et al. | Progress in air-processed perovskite solar cells: from crystallization to photovoltaic performance | |
Huang et al. | Boosting the ultra-stable unencapsulated perovskite solar cells by using montmorillonite/CH 3 NH 3 PbI 3 nanocomposite as photoactive layer | |
Choi et al. | Sn perovskite solar cells via 2D/3D bilayer formation through a sequential vapor process | |
Zhang et al. | Surfactant sodium dodecyl benzene sulfonate improves the efficiency and stability of air‐processed perovskite solar cells with negligible hysteresis | |
WO2015169243A1 (zh) | 金属氧化物-导电聚合物-醇组合物、其制备方法及应用 | |
EP3001439A1 (en) | Semiconductor film and application liquid for its fabrication | |
Rui et al. | Defect passivation and electrical conductivity enhancement in perovskite solar cells using functionalized graphene quantum dots | |
Hossain et al. | Fluoroarene derivative based passivation of perovskite solar cells exhibiting excellent ambient and thermo-stability achieving efficiency> 20% | |
KR20140044786A (ko) | 광기전력 전지 | |
Zhao et al. | Room-temperature-processed fullerene single-crystalline nanoparticles for high-performance flexible perovskite photovoltaics | |
US20210036250A1 (en) | Cathode Interface Modification Material Composition, Preparation Method and Use Thereof | |
Sun et al. | Enhanced photovoltage and stability of perovskite photovoltaics enabled by a cyclohexylmethylammonium iodide-based 2D perovskite passivation layer | |
Wang et al. | Large guanidinium cation enhance photovoltage for perovskite solar cells via solution-processed secondary growth technique | |
Gao et al. | Three-dimensional perovskite modulated by two-dimensional homologue as light-absorbing materials for efficient solar cells | |
Xu et al. | Room-temperature processed, air-stable and highly efficient graphene/silicon solar cells with an organic interlayer | |
EP2771920B1 (en) | Solution-processable tungsten oxide buffer layers and organic electronics comprising same | |
Luo | Applications in photovoltaics | |
Cao et al. | Ultraviolet‐Assisted Perovskite Crystallization for High‐Performance Solar Cells | |
Ebiç | Perovskite Güneş Hücreleri İçin EMIMBF4 İyonik Sıvı Katkılı SnO2 Elektron Transfer Tabakasının Düşük Sıcaklıkta Üretimi ve Optimizasyonu | |
Wang et al. | F-PEAI induced performance improvement for perovskite solar cells | |
Ishihara et al. | Highly Ordered Molecular Orientation in a Phthalocyanine Film Deposited on a Well-Polished Indium–Tin Oxide Substrate | |
Wang et al. | Building on soft hybrid perovskites: highly oriented metal oxides as electron transport and moisture resistant layers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: NANOGRADE AG, SWITZERLAND Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LUCHINGER, NORMAN ALBERT;HALIM, SAMUEL CLAUDE;SIGNING DATES FROM 20140807 TO 20140808;REEL/FRAME:033560/0925 |
|
AS | Assignment |
Owner name: AVANTAMA AG, SWITZERLAND Free format text: CHANGE OF NAME;ASSIGNOR:NANOGRADE AG;REEL/FRAME:042387/0788 Effective date: 20170313 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |